DE1213436B - Heat sensitive sheet material - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

B 41m

German class: 15 k-7/05

Number: 1213 436

File number: N 22558 VI b / 15 k

Filing date: December 31, 1962

Opening day: March 31, 1966

The present invention relates to a process employing thermosensitive materials and provides a new thermosensitive sheet material which is suitable for copying and recording and is characterized by the ability to reactivate when heated to an activation temperature of about 50 to 150 ⁰ C to form a mark of contrasting color. Sheet materials of this type are commonly used for thermographic copying processes, whereby a sheet is brought into close proximity to a graphic original and exposed with that original to infrared radiation which causes selective heating of the dark areas of the original sufficient to produce a copy thereof on the copy sheet to evoke. A more detailed description of this process is given in U.S. Patent 2,740,896. The sheet material according to this invention can also be used in registration devices in which marking is effected with a heated pen.

In the heat-sensitive sheet material of the present invention, the substances that are formed to form a colored compound react, incorporated into the leaf material in an intimate mixture. These substances that are here called precursors of the colored compound contain an ionizable, polyvalent compound Metal salt and an organic reagent (donor) that "donates" electrons, which works with the metal ions of the salt a clearly colored, polyvalent or covalent organometallic coordination complex forms. Typical representatives are metal salts, which are identified by spot reactions and reagents can be, as well as salts and organic reagents, by other similar known color-forming Reactions with the formation of a colored, polyvalent or covalent organometallic coordination complex meet.

In the heat-sensitive sheet material of the present invention, both precursors are considered physical different but intimately mixed components are introduced. One through warmth The reaction to be triggered between these components is brought about by making a solid stable Mixed crystal adduct is used, which consists of a bisphenol and a liquid organic ammonia derivative is formed, e.g. B. organic amines or amides, hydrazine derivatives and guanidine derivatives, to name just a few. Solid adducts of this type are well known (see, inter alia, USA patent specification 2 829 175).

In the heat-sensitive heat-sensitive sheet material of the present invention

Applicant:

Nashua Corporation, Nashua, N. H. (V. St A.)

Representative:

Dipl.-Ing. R. Beetz and Dipl.-Ing. K. Lamprecht, Patent Attorneys, Munich 22, Steinsdorfstr. 10

Named as inventor:

Michael F. Baumann, Hudson, N. H .;

William R. Lawton, Nashua, N. H. (V. St. A.)

Claimed priority:

V. St. v. America January 18, 1962 (167180)

Sheet material dissociates the mixed crystal adduct when heated and gives a liquid organic ammonia derivative free, which then acts as a carrier or mediator for the color-forming reaction between the precursors the colored compound serves, apparently by virtue of its ability, to dissociate the metal salt to cause and thus the metal salt and the organic reagent in reactive connection too bring. In this regard, the ammonia derivatives perform an essential physical function and do not appear to enter into any chemical reaction with any of the other color-forming reagents.

The color solid precursors should be lightly colored

be solid, non-hygroscopic and on the other hand stable under normal temperature and humidity conditions, ie under conditions that are actually encountered during storage, use and transport. The Mischkristalladdukt should likewise be dyed stably and easily and should also be dissociated or dissociable to thereby are at the desired activation temperature in the range of 50 to 150 ⁰ C, the ammonia derivative to specific liefern..Das bisphenol and ammonia derivatives thus in view of this Select criteria based on known or easily determined properties of materials of this type.

According to specific embodiments of the invention, the metal salt, the organic reagent and the mixed crystal adduct dispersed separately or together in a binder solution and as one or several layers on a piece of paper or other basic

609 540/149

3 4

surfaces applied by common methods. This mixture is dispersed in the same manner as the relative proportions and / or proportions of the dye dispersions prepared above.
Precursors (metal salt and organic reagent) A mixture of the three dispersions in should be such that a mutual reaction occurs in the proportions of 3 parts of dispersion A, five, with a total concentration of 5 parts of dispersion B and 2 parts of dispersion C, which is sufficient to put a clear color contrast marking. After careful mixing, the mixture will produce when the sheet material is heated. The usual way on a sheet of smooth or amount of the mixed crystal adduct should be applied sufficiently transparent paper, the weight of which is enough ammonia derivative as a reaction 40.7 g / m ² , the coating to produce a weight of carrier and a Has color reaction between the io 6.43 g / m ² . The coated paper will cause color precursors. These quantities can be dried in the air and can be determined in a registration through routine tests. Although the device is used with a heated pen, the amount of organic ammonia used, e.g. B. in a recorder for recording derivatives depending on the specially selected electrocardiograms with a character speed-color precursors can vary considerably, was 15 speed of about 250 to 760 cm per second. The sheet found that the best results obtained material can also be used for thermographic processes if the ammonia derivative are used in the same amount, e.g. B. in a commercially available or at least about 5% of the weight of the embossing ■ copier,
sensors is provided. Comparative tests were used to determine

The following examples describe in detail that, if Dispersion A and Combi are omitted, various embodiments of the invention. nation of 5 parts of dispersion B and 2 parts of the

Dispersion C and application of this mixture in the

For example, in the same way as in Example 1, no sheet material

which is thermographically sensitive.

A mixed crystal adduct is first formed by grain 25

combination of the following components: Example2

Tetrachlorobisphenol A. (TCBA) ..... 183g Following the procedure of Example 1,

Ethanolamine (ÄA) 61 g a mixed crystal adduct from a combination of

Toluene 364 g 30 gender ingredients made:

_#g The TCBA is dissolved in toluene at about 65 ° C, the tetrachlorobisphenol A (TCBA) ..... 183 g

Ethanolamine added and diethanolamine (DÄA) 105 g for 30 minutes

touched. The mixture is cooled to about -35 ° C. Toluene 364 2
and for 14 hours (overnight) at this 35

Temperature was maintained to give a _{precipitate, the} f _it te crystalline product is the mixed crystal forms. This is filtered off, carefully washed with η-hexane adduct TCBA / DÄA with a melting point of at room temperature and dried. 151 _s FJJ 153 ⁰ C.
The solid crystalline product is the mixed crystal adduct of tetrachlorobisphenol A and ethanolamine 40 A. A dispersion is made from:
(TCBA / ÄA) and has a melting point of 96 TCBA / DÄA 10 parts by weight

Ethyl hydroxyethyl cellulose

A. It is a mixture of the following ingredients (ÄHÄC) 2.5 parts by weight

parts made: ₄₅ hexane 86 parts by weight

TCBA / ÄA 10 g methyl alcohol 2 parts by weight

Polyvinyl butyral 2.5 g _The ingredients are placed in a ball mill

Trichlorethylene 87.5 g and ground overnight at 5 ° C.

The mixture is placed in a ball mill and 50 B. A second dispersion is made, consisting

Milled overnight at 5 ° C. the end:

B. A second dispersion is made, containing 5 parts by weight of diphenyl carbazide

consisting of: ÄHÄC 2.5 parts by weight

Dithiooxamide 55 ■ η-hexane 86 parts by weight

(Rubeanic acid) 2.5 parts by weight of ethyl alcohol 2 parts by weight

Polyvinyl butyral 2.5 parts by weight

Trichlorethylene 95 parts by weight _u ? ™ J? ^emis t ^{wkd in a} ball mill overnight

. ground at 5 C.

The mixture is also placed in a ball mill 60. A thermally responsive sheet material

given and ground overnight at 5 ° C. produced by first having a 5%

Cadmium nitrate solution in a 40 to 60 weight

C. A third dispersion is made up consisting of a percent methanol-water mixture made of: smooth or transparent paper sheets of 40.7 g

Nickel oxalate 10 ^{parts by weight 6s} weight per square meter in one thickness (moist)

_,,. "," _R. ^. , of about 1 mm. After the sheet has dried

Polyvinyl butyral 2.5 _{parts by weight wkd a 6} o ^ _ge gelatin solution in a 40- to

Trichlorethylene 87.5 parts by weight 60 percent by weight methanol-water mixture in

5 6

a coating thickness of 2 mm (wet) applied. Use in compositions of the invention After the gelatin coating has dried, it will be suitable to fall dithioxalic acid and its potassium in a mixture consisting of 2 parts of the dispersion A salts; Biuret; 8-hydroxyquinoline; Benzoin oxime; and 1 part of Dispersion B, in a dry weight 2,2'-dipyridyl; Anthranilic acid; Pyrogallol; Alizarin; applied at about 7.1 g / m ² . After drying, 5 tannins; Carminic acid; Morin; 2,3-butanedione oxime obtained in a heat-sensitive sheet material, the thiocarbazide.

is suitable for copying and recording purposes. There are also many combinations of metals and

Spotting reagents, such as. B. those in the USA.

Example 3 patent specification 2 663 656 and also in Fig. 1,

ίο »Qualitative Analysis by Spot Tests« are listed, Following the procedure of Example 1, one becomes useful.

Mixed crystal adduct by combining the following other organic ammonia derivatives, which are in the

Constituent parts made: above explanatory and suggested to

compositions can be used are

Tetrachlorobisphenol A (TCBA) 183 g ₁₅ tetramethylguanidine, ethylethanolamine, phenyletha-

Dimethylformamide (DMF) Ti g nolamine, dibutylamine, hydrazine, N-2-hydroxy-ethyl-

Toluene 364 g 1-methyl-dodecylamine, formamide, piperidine, tri-

ethanolamine, cyclochexylamine and dimethylacetamide.

The solid crystalline product is the mixed crystal- Numerous other bisphenols can be used to form adduct TCBA / DMF with a melting point of 20 of the mixed crystal adduct of organic ammonia-60 up to 65 ° C. derivatives can be used, e.g. B. tetrabromobisphenol

A, Bithionol, Bisphenol A as well as others that are in the

A. A dispersion is prepared from: United States Patent _{No. 2,829,175 listed above.}

TCBA / DMF 10 g.

Vinyl toluene / butadiene resin (VT / But) .. 2.5 g ² 5 ^The variety of useful methods and processes

^ t 1 ^ 1 87 5 2 ^for applying the coating according to the invention

P ' ° composition is used in the previous

The mixture is placed in a ball mill and the ^{games are} explained. The specially indicated in these examples

Milled overnight at 5 ° C. applied coating technology can be used without loss of

30 speaking on activation of the resulting

B. A second dispersion is made by modifying sheet material.

consisting of: mixed crystal adducts that are used for a special

Iron (III) sulfate 5 g twist should be suitable with regard to the

VT / But 5 ε dissociation temperature can be selected by, 35 mixing the adduct with a mixture of nickel naphtha ^{Zi> g} oxalate and rubeanic acid in dry

The mixture is placed in a ball mill and condition and heat slowly until color is formed

Milled overnight at 5 ° C. can be determined. The mixed crystal adduct should

also in terms of its stability, color and

C. A third dispersion is prepared consisting of ₄₀ hygroscopic properties selected ^from: To give the paper the desired properties to gallic acid 5 g.

VT / But 5 g That described in the previous examples

Naühtha 25 2 sheet material has an activation temperature im

45 range from 50 to 15O ⁰ C, which is determined thereby

The mixture is placed in a ball mill and has been placed on a surface for 1 second Milled overnight at 5 ° C. applied and the lowest temperature at which a visible

A sheet bar that responds to heat and a clear change in color is produced in the material mentioned by first determining a mixture of areas. Although the invention has been described in equal parts of dispersion B and dispersion C 50 with reference to exemplary and preferably to a sheet of smooth, transparent paper, embodiments, the weight of which is 40.7 g / m ^a , in a coating modifications in Consider, without the frame, the weight of 7.8 g / m ^a . To rely on this coating invention. There are other color-forming, after drying, a top layer of dispersion A systems based on ionizable more is applied in an amount of 4.9 g / m ² . The devalued sheet material containing metal salts and organic reagents provides an effective, thermally known, polyvalent or covalent coordinate-sensitive copying or recording medium. Numerous other salts of polyvalent metals can produce a distinct coloration with such metals, and many of them will undoubtedly prove to be suitable for sheet material, such as nickel formate, 60 for the purposes of the invention . Cobalt oxalate, nickel sulfate, aluminum chloride, copper and other bisphenol compounds and organic amoxalate, lead chloride, zinc sulfate, manganese chloride, nickel monia derivatives can also be used, provided that tartrate, iron oxalate, barium chloride and chelates of a nickel chloride with compounds based on the criteria described how 1,3-propylene selection is made. Other constituents of diamine, tetramethylenediamine and diaminohexane can also be used. 65 parts are added to the coating, such. B. Anti-Unter the many organic reagents that form polyvalent metallics colored with adhesives, anti-fingerprint agents, antistatic polyvalent metal ions, fillers and coloring compounds, and anti-organic coordination complexes and which, if necessary, can also be other than parchment paper

Base sheet material can be used, such as regenerated cellulose, cellulose ester, other types of paper as well as plastics.

Claims (1)

Claim: Heat sensitive sheet material that is stable and slightly colored under normal conditions and at an activation temperature in the range from 50 to 150 ° C by visible and irreversible Transition to a contrasting color with the formation of a dye responds to heat, characterized in that the sheet material is a solid, stable, ionizable multivalent Metal salt and an organic reagent that interacts with the metal ions of the salt by covalent Coordinate bond between the metal ions and the reagent to form "a colored organometallic compound reacts, and also a solid, stable crystalline mixed crystal adduct of bisphenol and a liquid organic ammonia derivative, the salt and the reagent represent precursors of the colored compound and the adduct a dissociation temperature between 50 and 150 ° C, at which the liquid ammonia derivative to bring about the Reaction between salt and reagent is released. 609 540/149 3.66 © Bundesdruckerei Berlin